CN114300675B - Positive electrode material, preparation method thereof and water-based zinc ion battery - Google Patents
Positive electrode material, preparation method thereof and water-based zinc ion battery Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 69
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims description 67
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 57
- 229910052799 carbon Inorganic materials 0.000 claims description 56
- 239000011701 zinc Substances 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 48
- 239000011259 mixed solution Substances 0.000 claims description 48
- 238000000498 ball milling Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000010406 cathode material Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 235000013877 carbamide Nutrition 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 10
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- 229910052735 hafnium Inorganic materials 0.000 abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 abstract description 5
- -1 zinc acetate compound Chemical class 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052725 zinc Inorganic materials 0.000 description 14
- 239000003738 black carbon Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 7
- 229940010552 ammonium molybdate Drugs 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 229910003481 amorphous carbon Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000011163 secondary particle Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000004246 zinc acetate Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
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- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical class [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a positive electrode material, a preparation method thereof and a water-based zinc ion battery. The general formula of the positive electrode material is A x B y O 8 @C, wherein A is selected from one or more of Li, na, mg, ni, co, fe, cu, zn and Y, wherein x is 1-3, B is one or more of Ti, V, cr, mo, W, zr and Hf, and wherein Y is 2-3; the particle diameter of the positive electrode material is preferably 0.1 to 8. Mu.m, and the thickness of C in the positive electrode material is preferably 5 to 10nm. C in the positive electrode material is opposite to A x B y O 8 Coating, A x B y O 8 In a layered structure, zn can be made into 2+ At A x B y O 8 Middle-release embedding; and B is a metal element with multiple valence states, and can release multiple electrons in the charge and discharge process, so that the positive electrode material has higher specific capacity, the conductivity of the positive electrode material is improved, and the positive electrode material has high specific capacity, stable long-cycle performance and excellent rate capability.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a positive electrode material, a preparation method thereof and a water-based zinc ion battery.
Background
The lithium ion battery has high energy density, high power density, long service life and no memory effect, and is widely applied to large-scale energy storage equipment such as wearable portable intelligent equipment, electric automobiles, hybrid electric vehicles and the like. In fact, the flammability of the organic electrolyte of lithium ion batteries and the maldistribution and limitation of lithium resources present many safety hazards and economic challenges, making lithium ion battery technology less suitable for certain applications. The safety and low cost of aqueous zinc ion batteries, as compared to other prominent energy storage technologies, make them promising for applications in stationary energy storage systems such as power grids, household energy sources, energy storage power stations, etc. where mass energy density is less important.
The water-based zinc ion battery has the following advantages: 1. a higher standard potential for hydrogen (-0.76V) and a high overpotential; 2. the zinc metal anode is environment-friendly and corrosion-resistant; 3. the ionic conductivity of aqueous electrolytes is typically two orders of magnitude higher than that of organic systems and is not flammable; 4. compared with a lithium ion battery, the water-based zinc ion battery can be easily manufactured in an air environment, and the overall production cost of the water-based zinc ion battery is greatly reduced. In addition, the zinc metal is directly used as a negative electrode, and has higher energy density (5855 mAh cm -3 ) This means that a proper positive electrode material is sought to be directly matched with a zinc negative electrode to form a high-performance water-based zinc ion battery.
Disclosure of Invention
The application mainly aims to provide a positive electrode material, a preparation method thereof and a water-based zinc ion battery, so as to solve the problems of poor multiplying power performance and serious specific capacity attenuation in the charge-discharge cycle process of the water-based zinc ion battery in the prior art.
In order to achieve the above object, according to one aspect of the present application, there is provided a positive electrode material having the general formula A x B y O 8 @C, wherein A is selected from one or more of Li, na, mg, ni, co, fe, cu, zn and Y, wherein x is 1-3, B is one or more of Ti, V, cr, mo, W, zr and Hf, and A x B y O 8 Having layersA crystalline structure, wherein y is 2 to 3; the particle diameter of the positive electrode material is preferably 0.1 to 8. Mu.m, and the thickness of C in the positive electrode material is preferably 5 to 10nm.
Further, A x B y O 8 Is Zn 2 Mo 3 O 8 、Zn 2 V 3 O 8 、LiYMo 3 O 8 、CuTi 3 O 8 @C or LiFeMo 3 O 8 。
In order to achieve the above object, according to one aspect of the present application, there is provided a method for preparing the above positive electrode material, comprising: step S1, mixing an A source compound, a B source compound, an organic carbon source and water to obtain a mixed solution, and heating the mixed solution to obtain wet sol, wherein the A source compound is selected from one or more elements of Li, na, mg, ni, co, mn, fe, cu, zn and Y, the B source compound is Ti, mn, cr, mo, W, zr or Hf, and the element A in the A source compound is different from the element B in the B source compound; step S2, drying the wet sol to obtain xerogel; step S3, performing first sintering on the xerogel in nitrogen or inert atmosphere to obtain a sintered product; and S4, performing second sintering on the sintered product in nitrogen or inert atmosphere to obtain the anode material, wherein the sintering temperature of the first sintering is lower than that of the second sintering.
Further, step S3 further comprises wet grinding the sintered product after the first sintering to obtain precursor powder with the particle size of 0.5-4 mu m; and/or after step S4, the preparation method further comprises wet ball milling the cathode material, preferably, the solvent used for wet ball milling is anhydrous ethanol and/or acetone.
Further, the A source compound is one or more of an oxide, a hydroxide, a carbonate, a sulfate, an acetate, a nitrate and an ammonium salt of A; the B source compound is one or more of oxide, ammonium salt, nitrate and sulfate of B.
Further, the organic carbon source is one or more of citric acid, glucose, sucrose, maltose, ascorbic acid, starch, urea, aniline and phenolic resin.
Further, the molar ratio of the element A in the source A compound to the element B in the source B compound is (1-3): (2-3), preferably, the mass content of the A source compound in the mixed solution is 28-40 wt.%, and the mass content of the organic carbon source is 0.1-10 wt.%.
Further, step S1 includes: mixing the source A compound and the source B compound with water, and preheating to obtain a first mixed solution, wherein the preferable preheating temperature is 80-90 ℃, and the preheating time is 0.5-1 h; mixing the first mixed solution with an organic carbon source to obtain a mixed solution; heating the mixed solution to obtain wet sol; preferably, the heating temperature is 80-90 ℃; preferably, the drying temperature is 100-170 ℃ and the drying time is 4-6 h.
Further, the temperature of the first sintering is 300-400 ℃, the time of the first sintering is 2-4 h, the temperature of the second sintering is 500-900 ℃, and the time of the second sintering is 5-20 h.
According to another aspect of the application, there is provided an aqueous zinc ion battery comprising a positive electrode, a negative electrode, and an electrolyte, the positive electrode comprising the positive electrode material.
By applying the technical scheme of the application, the C in the positive electrode material is prepared in the way of coating the A x B y O 8 Coating, wherein A x B y O 8 Has a layered crystal structure, and can make Zn 2+ At A x B y O 8 Middle-release embedding; and B selects metal elements with multiple valence states, and can release multiple electrons in the charge and discharge process, so that the positive electrode material has higher specific capacity, and the C coating layer improves the conductivity of the positive electrode material, so that the positive electrode material has high specific capacity, stable long-cycle performance and excellent rate capability.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 shows an implementation of the applicationCarbon coated product Zn of example 1 2 Mo 3 O 8 XRD pattern of @ C;
fig. 2 shows an SEM image of the positive electrode material of example 1 of the present application;
fig. 3 shows a TEM image of the positive electrode material of example 1 of the present application;
fig. 4 shows a charge-discharge curve of the aqueous zinc ion battery of example 1 of the present application;
fig. 5 shows a cycle performance chart of the aqueous zinc ion battery of example 1 of the present application.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
As analyzed by the background art, the water-based zinc ion battery in the prior art has the problems of poor rate capability and serious specific capacity attenuation during charge and discharge cycles. In order to solve the problem, the application provides a positive electrode material, a preparation method thereof and an aqueous zinc ion battery.
In one exemplary embodiment of the present application, a positive electrode material is provided having the general formula A x B y O 8 @C, wherein A is selected from one or more of Li, na, mg, ni, co, mn, fe, cu, zn and Y, wherein x is 1-3, B is one or more of Ti, mn, cr, mo, W, zr and Hf, and A x B y O 8 Has a layered crystal structure, wherein y is 2 to 3.
C in the positive electrode material is coated with A x B y O 8 Coating, wherein A x B y O 8 Has a layered crystal structure, and can make Zn 2+ At A x B y O 8 Middle-release embedding; and B selects metal elements with multiple valence states, and can release multiple electrons in the charge and discharge process, so that the positive electrode material has higher specific capacity, and the C coating layer improves the conductivity of the positive electrode material, so that the positive electrode material has high specific capacity, stable long-cycle performance and excellent multiplying powerCan be used.
To further increase the compacted density and shorten Zn 2+ The particle diameter of the positive electrode material is controlled to be 0.1-8 mu m, and the dynamic performance of the material is improved. To balance conductivity and make Zn 2+ At A x B y O 8 The thickness of C in the positive electrode material is more preferably 5 to 10nm.
In some embodiments, the positive electrode material may be Zn 2 Mo 3 O 8 ，Zn 2 V 3 O 8 ，LiYMo 3 O 8 ，CuTi 3 O 8 @C，LiFeMo 3 O 8 . Especially when the positive electrode material is Zn 2 Mo 3 O 8 ，Zn 2 V 3 O 8 The cycle performance and rate characteristics are improved particularly when the battery is used.
In another exemplary embodiment of the present application, there is provided a method for preparing a positive electrode material of any one of the above, the method comprising: step S1, mixing an A source compound, a B source compound, an organic carbon source and water to obtain a mixed solution, and heating the mixed solution to obtain wet sol, wherein the A source compound is selected from one or more elements of Li, na, mg, ni, co, mn, fe, cu, zn and Y, the B source compound is Ti, mn, cr, mo, W, zr or Hf, and the element A in the A source compound is different from the element B in the B source compound; step S2, drying the wet sol to obtain xerogel; step S3, performing first sintering on the xerogel in nitrogen or inert atmosphere to obtain a sintered product; and S4, performing second sintering on the sintered product in nitrogen or inert atmosphere to obtain the anode material, wherein the sintering temperature of the first sintering is lower than that of the second sintering.
The preparation method of the application realizes the uniform mixing of raw material atoms or molecular levels under the liquid phase, thereby avoiding the formation of impurity phases caused by the uneven mixing of raw materials, having simple synthesis process and being easy to realize large-scale industrial production; in the preparation process, the amorphous carbon is coated on the surface of the positive electrode material by adding an organic carbon source into the system, so that the conductivity of the positive electrode material is improved, the electron transmission path is optimized, the dynamic performance of the positive electrode material is improved, and the problems of low specific capacity attenuation and poor multiplying power performance of the battery are further effectively improved in the charge-discharge cycle process. Meanwhile, the secondary sintering can enable the reaction to be more sufficient, and the generation of impurity phases is reduced. Specifically, the xerogel releases gas through the first sintering, which is beneficial to stabilizing the oxygen partial pressure and the air tightness of the furnace body in the subsequent high-temperature sintering process; in addition, the xerogel is decomposed into metal oxide through the first sintering to obtain precursor powder, and the distance from metal atoms to the solid phase reaction interface of the precursor powder is shortened in the subsequent high-temperature sintering process, so that the high-temperature sintering time is shortened, and the energy consumption can be reduced.
In some embodiments, step S3 further comprises wet milling the sintered product after the first sintering to obtain a precursor powder having a particle size of 0.5-4 μm; and/or after step S4, the above preparation method further comprises performing wet ball milling on the cathode material, and preferably, the solvent used for the wet ball milling is anhydrous ethanol and/or acetone. Decomposing the xerogel into metal oxide through first sintering, and fully grinding and uniformly mixing to obtain precursor powder; in the subsequent high-temperature sintering process, the distance from metal atoms to the solid-phase reaction interface of the metal atoms is shortened, so that the high-temperature sintering time is shortened, and the energy consumption can be reduced. The particle size of the secondary particles can be reduced by wet ball milling, thereby shortening Zn 2+ Thereby improving the rate performance of the cathode material.
Referring to the cathode materials commonly used in the art, in some embodiments, the a source compound described above is one or more of an oxide, hydroxide, carbonate, sulfate, acetate, nitrate, and ammonium salt of a; the B source compound is one or more of oxide, ammonium salt, nitrate and sulfate of B. The above-mentioned compounds can retain A element, B element and oxygen element in the positive electrode material in the course of sintering, and other carbon element, nitrogen element and sulfur element, etc. can be burnt out.
To increase the conductivity of the positive electrode material, and further increase the specific capacity of the positive electrode material, in some embodiments, the organic carbon source is one or more of citric acid, glucose, sucrose, maltose, ascorbic acid, starch, urea, aniline, and phenolic resin, which not only provides carbon in the positive electrode material, but also serves to sequester metal ions during mixing.
In order to improve the stability and conductivity of the positive electrode material, the molar ratio of the element A in the source compound A to the element B in the source compound B is (1-3): (2-3). In order to effectively improve the conductivity of the cathode material and avoid excessive organic carbon sources from obstructing the transmission of lithium ions, the mass content of the A source compound in the mixed solution is preferably 28-40 wt.% and the mass content of the organic carbon source is 0.1-10 wt.%.
In order to coat amorphous carbon on the surface of the cathode material more uniformly, in some embodiments, the step S1 includes: mixing the source A compound and the source B compound with water, and preheating to obtain a first mixed solution, wherein the preferable preheating temperature is 80-90 ℃, and the preheating time is 0.5-1 h; mixing the first mixed solution with an organic carbon source to obtain a mixed solution; and heating the mixed solution to obtain wet sol. The A source compound and the B source compound are mixed with water, so that the A source compound and the B source compound can be fully mixed, and amorphous carbon is uniformly coated on the anode material.
In order to remove excess water from the mixed solution, in some embodiments, the temperature of heating is 80-90 ℃.
In order to remove the moisture from the wet sol while avoiding disruption of the already formed homogeneous structure in the wet sol, in some embodiments, the drying is carried out at a temperature of 100 to 170 ℃ for a period of 4 to 6 hours.
In order to control the coating speed of the amorphous carbon and to increase the density of the coating, the amorphous carbon is tightly coated on the surface of the positive electrode material, and in some embodiments, the temperature of the first sintering is 300-400 ℃, the time of the first sintering is 2-4 hours, preferably the temperature of the second sintering is 500-900 ℃, and the time of the second sintering is 5-20 hours. The application carries out secondary sintering on the xerogel, avoids the generation of heterogeneous phase in the sintering process as far as possible, and can reduce the synthesis temperature of the material and the high-temperature sintering time.
In yet another exemplary embodiment of the present application, an aqueous zinc ion battery is provided, comprising a positive electrode, a negative electrode, and an electrolyte, the positive electrode comprising the positive electrode material described above. The water-based zinc ion battery has high specific capacity, stable long-cycle performance and excellent rate performance.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
Example 1
(1) Sequentially adding a zinc acetate compound and an ammonium molybdate compound into deionized water according to the molar ratio of zinc to molybdenum being 2:3, magnetically stirring, and heating in a water bath at 90 ℃ for 0.5h to obtain a first mixed solution; mixing the first mixed solution with soluble organic carbon source citric acid to obtain a mixed solution, wherein the content of the organic carbon source citric acid in the mixed solution is 3wt.%.
(2) Stirring was continued at a temperature of 90 ℃ until excess water evaporated, forming a wet sol.
(3) The wet sol was dried in an oven at 150 ℃ for 4 hours to give a xerogel.
(4) And (3) placing the xerogel in a mortar for full and uniform grinding, transferring the mixture into a tube furnace, performing first sintering for 2 hours at 350 ℃ under the protection of argon to obtain a sintered product, and performing wet grinding on the sintered product to obtain precursor powder with the particle size of 0.5-4 mu m.
(5) Transferring the precursor powder into a tube furnace again, and performing secondary sintering at 750 ℃ for 5 hours under the protection of argon to obtain a black carbon-coated product Zn 2 Mo 3 O 8 @C, carbon coated product Zn 2 Mo 3 O 8 The XRD pattern of @ C is shown in FIG. 1. Coating carbon with Zn 2 Mo 3 O 8 Sieving @ C, performing wet ball milling, wherein the solvent used in the wet ball milling is absolute ethyl alcohol to reduce Zn in the carbon-coated product 2 Mo 3 O 8 The secondary particle size of @ C gives a positive electrode material having a particle size of 0.4 to 2 μm, and an SEM image of the positive electrode material is shown in FIG. 2As shown in FIG. 2, the particles are irregular in shape and have a size of 0.5-2 μm, the TEM image of the positive electrode material is shown in FIG. 3, and the amorphous carbon layer is coated on the surface of the particles and has a thickness of 5-10 nm as apparent from FIG. 3.
Example 2
(1) Sequentially adding a zinc acetate compound and an ammonium molybdate compound into deionized water according to the molar ratio of zinc to molybdenum being 2:3, magnetically stirring, and heating in a water bath at 90 ℃ for 0.5h to obtain a first mixed solution; mixing the first mixed solution with soluble organic carbon source citric acid to obtain a mixed solution, wherein the content of the organic carbon source citric acid in the mixed solution is 1wt.%.
(2) Stirring was continued at a temperature of 90 ℃ until excess water evaporated, forming a wet sol.
(3) The wet sol was dried in an oven at 150 ℃ for 4 hours to give a xerogel.
(4) And (3) placing the xerogel in a mortar for full and uniform grinding, transferring the mixture into a tube furnace, performing first sintering for 2 hours at 350 ℃ under the protection of argon to obtain a sintered product, and performing wet grinding on the sintered product to obtain precursor powder with the particle size of 0.5-4 mu m.
(5) Transferring the precursor powder into a tube furnace again, and performing secondary sintering at 750 ℃ for 5 hours under the protection of argon to obtain a black carbon-coated product Zn 2 Mo 3 O 8 And @ C. Coating carbon with Zn 2 Mo 3 O 8 Sieving @ C, performing wet ball milling, wherein the solvent used in the wet ball milling is absolute ethyl alcohol to reduce Zn in the carbon-coated product 2 Mo 3 O 8 And (3) the secondary particle size of the @ C to obtain the positive electrode material.
Example 3
(1) Sequentially adding a zinc acetate compound and an ammonium molybdate compound into deionized water according to a molar ratio of zinc to molybdenum of 2:3, magnetically stirring, and heating in a water bath at 90 ℃ for 0.5h to obtain a first mixed solution; mixing the first mixed solution with soluble organic carbon source citric acid to obtain a mixed solution, wherein the content of the organic carbon source citric acid in the mixed solution is 5wt.%.
(2) Stirring was continued at a temperature of 90 ℃ until excess water evaporated, forming a wet sol.
(3) The wet sol was dried in an oven at 150 ℃ for 4 hours to give a xerogel.
(4) And (3) placing the xerogel in a mortar for full and uniform grinding, transferring the mixture into a tube furnace, performing first sintering for 2 hours at 350 ℃ under the protection of argon to obtain a sintered product, and performing wet grinding on the sintered product to obtain precursor powder with the particle size of 0.8-3 mu m.
(5) Transferring the precursor powder into a tube furnace again, and performing secondary sintering at 750 ℃ for 5 hours under the protection of argon to obtain a black carbon-coated product Zn 2 Mo 3 O 8 And @ C. Coating carbon with Zn 2 Mo 3 O 8 Sieving @ C, performing wet ball milling, wherein the solvent used in the wet ball milling is absolute ethyl alcohol to reduce Zn in the carbon-coated product 2 Mo 3 O 8 The secondary particle size of @ C, the particle size of the obtained positive electrode material is 0.3-2 mu m.
Example 4
Unlike example 1, a lithium carbonate compound, a yttrium oxide compound and an ammonium molybdate compound were sequentially added to deionized water in a molar ratio of lithium, yttrium and molybdenum of 1:1:3, to finally obtain a black carbon-coated product LiYMo 3 O 8 @C。
Example 5
Unlike example 1, a copper nitrate compound and a titanium oxide compound were sequentially added to deionized water at a molar ratio of copper to titanium of 1:3, to finally obtain a black carbon-coated product CuTi 3 O 8 @C。
Example 6
Unlike example 1, zinc nitrate and ammonium vanadate compounds were added sequentially to deionized water at a molar ratio of zinc to vanadium of 2:3, to finally obtain black carbon-coated product Zn 2 V 3 O 8 @C。
Example 7
Unlike example 1, lithium carbonate compound, ferric nitrate, ammonium vanadate compound were mixed in a molar ratio of lithium, iron and vanadium of 1:1:3 sequentially adding the carbon-coated material into deionized water to finally obtain black carbon-coated product LiFeMo 3 O 8 @C。
Example 8
Unlike example 1, zinc acetate compound and ammonium molybdate compound were sequentially added to deionized water at a molar ratio of zinc to molybdenum of 1:0.9, finally obtaining black carbon-coated product ZnMo 0.9 O 8 @C, wherein ZnMo 0.9 O 8 Comprises Zn 2 Mo 3 O 8 And ZnO, znO being present as a hetero-phase.
Example 9
Unlike example 1, the organic carbon source of step (1) is glucose.
Example 10
Unlike example 1, the organic carbon source of step (1) is ascorbic acid.
Example 11
Unlike example 1, in step (1), the content of the organic carbon source citric acid in the mixed solution was 10wt.%.
Example 12
Unlike example 1, in step (1), the content of the organic carbon source citric acid in the mixed solution was 0.1wt.%.
Example 13
Unlike example 1, in step (1), the content of the organic carbon source citric acid in the mixed solution was 12wt.%.
Example 14
Unlike example 1, in step (4), the first sintering was performed at 300 ℃ for 4 hours; in step (5), the second sintering is performed at 500 ℃ for 20 hours.
Example 15
Unlike example 1, in step (4), the first sintering is performed at 400 ℃ for 4 hours; the second sintering is carried out at 900℃for 5h.
Example 16
Unlike example 1, in step (4), the first sintering was performed at 200 ℃.
Example 17
Unlike example 1, in step (4), the first sintering was performed at 450 ℃.
Example 18
Unlike example 1, in step (5), the second sintering was performed at 450 ℃.
Example 19
Unlike example 1, in step (5), the second sintering was performed at 950 ℃.
Example 20
(1) Sequentially adding a zinc acetate compound and an ammonium molybdate compound into deionized water according to a molar ratio of zinc to molybdenum of 2:3, magnetically stirring, and heating in a water bath at 90 ℃ for 0.5h to obtain a first mixed solution; mixing the first mixed solution with soluble organic carbon source citric acid to obtain a mixed solution, wherein the content of the organic carbon source citric acid in the mixed solution is 3wt.%.
(2) Stirring was continued at a temperature of 90 ℃ until excess water evaporated, forming a wet sol.
(3) The wet sol was dried in an oven at 150 ℃ for 4 hours to give a xerogel.
(4) And (3) placing the xerogel in a mortar, fully and uniformly grinding, transferring to a tube furnace, and performing first sintering for 2 hours at 350 ℃ under the protection of argon to obtain a sintered product.
(5) The sintered product is subjected to secondary sintering at 750 ℃ for 5 hours to obtain black carbon-coated product Zn 2 Mo 3 O 8 And @ C. Coating carbon with Zn 2 Mo 3 O 8 Sieving @ C, performing wet ball milling, wherein the solvent used in the wet ball milling is absolute ethyl alcohol to reduce Zn in the carbon-coated product 2 Mo 3 O 8 And (3) the secondary particle size of the @ C to obtain the positive electrode material.
Example 21
Unlike example 1, the carbon-coated product Zn was as follows 2 Mo 3 O 8 No wet ball milling was performed after sieving @ C.
Comparative example 1
Unlike example 1, this comparative example did not add any carbon source-coated transition metal oxide Zn 2 Mo 3 O 8 。
Comparative example 2
(1) Sequentially adding a zinc acetate compound and an ammonium molybdate compound into deionized water according to a molar ratio of zinc to molybdenum of 2:3, magnetically stirring, and heating in a water bath at 90 ℃ for 0.5h to obtain a first mixed solution; mixing the first mixed solution with soluble organic carbon source citric acid to obtain a mixed solution, wherein the content of the organic carbon source citric acid in the mixed solution is 3wt.%.
(2) Stirring was continued at a temperature of 90 ℃ until excess water evaporated, forming a wet sol.
(3) The wet sol was dried in an oven at 150 ℃ for 4 hours to give a xerogel.
(4) Placing the xerogel in a mortar, fully and uniformly grinding, transferring to a tube furnace, and sintering at 750 ℃ for 5 hours under the protection of argon to obtain a black carbon-coated product Zn 2 Mo 3 O 8 @ C, coating carbon with product Zn 2 Mo 3 O 8 Sieving @ C, performing wet ball milling, wherein the solvent used in the wet ball milling is absolute ethyl alcohol to reduce Zn in the carbon-coated product 2 Mo 3 O 8 The secondary particle size of @ C gives a positive electrode material having a particle size of 0.5 to 4 μm.
Comparative example 3
Unlike example 4, no organic carbon source was added during the synthesis to give LiYmo as a product 3 O 8 。
Comparative example 4
Unlike example 5, no organic carbon source was added during the synthesis to give CuTi as a product 3 O 8 。
Comparative example 5
Unlike example 7, no organic carbon source was added during the synthesis to give LiFeMo as a product 3 O 8 。
The application is respectivelyThe cathode materials synthesized in examples and comparative examples were used as aqueous zinc ion battery cathode materials. The electrochemical performance of the CR2032 button cell is tested, wherein the anode is a mixture (mass ratio of 8:1:1) of anode materials, acetylene black and polyvinylidene fluoride synthesized in each example and comparative example, the cathode is a high-purity metal zinc sheet, and the electrolyte is 3mol/L Zn (CF) 3 SO 3 ) 2 The solution and the isolating film are glass fiber. The constant-current charge-discharge voltage range is 0.05-1.7V (vs. Zn) 2+ /Zn)。
The battery assembled from the positive electrode material of example 1 had a current density of 0.1. 0.1A g -1 The lower charge-discharge curve is shown in FIG. 4, and the specific capacities of the first charge and discharge are 188mAh g respectively -1 And 191mAh g -1 The capacity of the second charge and discharge is 199mAh g -1 And 197mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the The corresponding cycle performance is shown in FIG. 5, and after 100 cycles, the discharge capacity is still 202mAh g -1 And shows stable circulation stability. In the current density range of 0.1A g -1 ～2A g -1 And (3) performing a rate performance test.
TABLE 1
From the data in table 1 and fig. 4 and 5, the electrode material is gradually activated through deep charge and discharge process, so that the specific capacity thereof is gradually increased. When the content of the organic carbon source citric acid is properly increased, the first charge capacity, the first coulombic efficiency, the cycle performance and the multiplying power of the sample are obviously improved; when the content of the organic carbon source citric acid is excessively increased, the cycle performance and the rate performance of the organic carbon source citric acid are reduced to a certain extent. Thicker carbon layers can hinder the transport of lithium ions and simultaneously reduce the overall specific capacity of the zinc molybdate positive electrode material.
From example 1 and comparative example 1, the cathode materials prepared in the sol-gel synthesis method can improve electron conductivity of significant materials, optimize electron transport paths, and exhibit stable long-cycle performance.
From examples 1 and 20, zn was not treated by wet ball milling 2 Mo 3 O 8 The @ C electrode had a somewhat poorer rate capability, which can be attributed to the production of Zn of smaller particle size by wet ball milling treatment 2 Mo 3 O 8 @C, which is favorable for shortening Zn in the charge and discharge process 2+ Thereby improving the dynamic performance of the material and showing excellent rate performance.
From the results of example 1 and comparative example 2, the presence of hetero-phase ZnO in the positive electrode material of comparative example 2 suggests that the reaction is incomplete due to the high temperature sintering performed only once in comparative example 2, and thus it is necessary to lengthen the reaction time.
From examples 4,5, 7 and comparative examples 3-5, the materials of examples 4,5 and 7 themselves do not contain zinc, the positions in which the layered structure can intercalate during the first discharge are limited, whereas the material of example 1 itself contains zinc, and the zinc ions in the layered structure can deintercalate during the first charge, providing more positions for intercalation of zinc ions. This also well explains that examples 4,5 and 7 have far less electrochemical performance than example 1. The zinc storage properties of the transition metal oxide electrode materials themselves were further demonstrated to be poor as compared to the electrochemical properties of comparative examples 3 to 5, but after the carbon modification according to the present application, the cycle capacity retention rate was significantly improved relative to that before the modification.
From the above description, it can be seen that the above embodiments of the present application achieve the following technical effects: the preparation method of the application realizes the uniform mixing of raw material atoms or molecular levels under the liquid phase, thereby avoiding the formation of impurity phases caused by the uneven mixing of raw materials, having simple synthesis process and being easy to realize large-scale industrial production; in the preparation process, the amorphous carbon is coated on the surface of the positive electrode material by adding an organic carbon source into the system, so that the conductivity of the positive electrode material is improved, the electron transmission path is optimized, the dynamic performance of the positive electrode material is improved, and the problems of low specific capacity attenuation and poor multiplying power performance of the battery are further effectively improved in the charge-discharge cycle process. Meanwhile, secondary sintering can fully react and reduce impurity phases; specifically, the xerogel releases gas through the first sintering, which is favorable for stabilizing the oxygen partial pressure and the air tightness of a furnace body in the subsequent high-temperature sintering process, in addition, the xerogel is decomposed into metal oxide through the first sintering to obtain precursor powder, and the distance from metal atoms to a solid-phase reaction interface of the precursor powder is favorable for shortening the high-temperature sintering time in the subsequent high-temperature sintering process, so that the energy consumption can be reduced.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A zinc ion battery positive electrode material is characterized in that the general formula of the zinc ion battery positive electrode material is A x B y O 8 @C, wherein A x B y O 8 Is Zn 2 Mo 3 O 8 、Zn 2 V 3 O 8 、LiYMo 3 O 8 、CuTi 3 O 8 Or LiFeMo 3 O 8 The A is x B y O 8 Has a layered crystal structure; the thickness of C in the zinc ion battery anode material is 5-10 nm; the preparation method of the zinc ion battery anode material comprises the following steps:
step S1, mixing an A source compound, a B source compound and water, and preheating to obtain a first mixed solution, wherein the preheating temperature is 80-90 ℃ and the preheating time is 0.5-1 h; mixing the first mixed solution with an organic carbon source to obtain a second mixed solution; heating the second mixed solution to obtain wet sol; the heating temperature is 80-90 ℃; the A source compound is selected from one or more elements of Li, fe, cu, zn and Y, and the B source compound is one or more elements of Ti, V and Mo;
step S2, drying the wet sol to obtain xerogel; the drying temperature is 100-170 ℃ and the drying time is 4-6 hours;
step S3, performing first sintering on the xerogel in nitrogen or inert atmosphere to obtain a sintered product; the temperature of the first sintering is 300-400 ℃ and the time is 2-4 hours;
step S4, performing second sintering on the sintered product in nitrogen or inert atmosphere to obtain the zinc ion battery anode material; the temperature of the second sintering is 500-900 ℃ and the time is 5-20 h;
step S3 further comprises wet grinding the sintered product after the first sintering to obtain precursor powder; and/or after the step S4, the preparation method further comprises wet ball milling of the zinc ion battery anode material.
2. The zinc ion battery positive electrode material according to claim 1, wherein the particle size of the zinc ion battery positive electrode material is 0.1-8 μm.
3. The zinc ion battery positive electrode material according to claim 1, wherein the particle size of the precursor powder is 0.5-4 μm.
4. A zinc ion battery cathode material according to claim 3, wherein the solvent used for the wet ball milling is anhydrous ethanol and/or acetone.
5. The zinc-ion battery positive electrode material according to claim 1, wherein the a source compound is one or more of an oxide, hydroxide, carbonate, sulfate, acetate, nitrate and ammonium salt of a; the B source compound is one or more of oxide, ammonium salt, nitrate and sulfate of B.
6. The zinc-ion battery cathode material according to claim 1, wherein the organic carbon source is one or more of citric acid, glucose, sucrose, maltose, ascorbic acid, starch, urea, aniline, and phenolic resin.
7. The zinc-ion battery positive electrode material according to any one of claims 1 to 4, wherein the molar ratio of the element a in the a source compound to the element B in the B source compound is (1 to 3): (2-3), wherein the mass content of the A source compound in the second mixed solution is 28-40 wt%, and the mass content of the organic carbon source is 0.1-10 wt%.
8. A method for preparing the zinc-ion battery cathode material according to any one of claims 1 to 7, characterized in that the method for preparing the zinc-ion battery cathode material comprises:
step S1, mixing an A source compound, a B source compound and water, and preheating to obtain a first mixed solution, wherein the preheating temperature is 80-90 ℃ and the preheating time is 0.5-1 h; mixing the first mixed solution with an organic carbon source to obtain a second mixed solution; heating the second mixed solution to obtain wet sol; the heating temperature is 80-90 ℃; the A source compound is selected from one or more elements of Li, fe, cu, zn and Y, and the B source compound is one or more elements of Ti, V and Mo;
step S2, drying the wet sol to obtain xerogel; the drying temperature is 100-170 ℃ and the drying time is 4-6 hours;
step S3, performing first sintering on the xerogel in nitrogen or inert atmosphere to obtain a sintered product; the temperature of the first sintering is 300-400 ℃ and the time is 2-4 hours;
step S4, performing second sintering on the sintered product in nitrogen or inert atmosphere to obtain the zinc ion battery anode material; the temperature of the second sintering is 500-900 ℃ and the time is 5-20 h;
step S3 further comprises wet grinding the sintered product after the first sintering to obtain precursor powder; and/or after the step S4, the preparation method further comprises wet ball milling of the zinc ion battery anode material.
9. The method for preparing a positive electrode material of a zinc ion battery according to claim 8, wherein the a source compound is one or more of an oxide, hydroxide, carbonate, sulfate, acetate, nitrate and ammonium salt of a; the B source compound is one or more of oxide, ammonium salt, nitrate and sulfate of B; and/or the number of the groups of groups,
the organic carbon source is one or more of citric acid, glucose, sucrose, maltose, ascorbic acid, starch, urea, aniline and phenolic resin; and/or the number of the groups of groups,
the molar ratio of the element A in the source A compound to the element B in the source B compound is (1-3): (2-3), wherein the mass content of the A source compound in the second mixed solution is 28-40 wt%, and the mass content of the organic carbon source is 0.1-10 wt%.
10. An aqueous zinc ion battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises the zinc ion battery positive electrode material according to any one of claims 1 to 7 or the zinc ion battery positive electrode material prepared by the preparation method of the zinc ion battery positive electrode material according to claim 8 or 9.
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